EP3828961B1 - Lithiumprimärzelle und intelligenter zähler - Google Patents

Lithiumprimärzelle und intelligenter zähler Download PDF

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Publication number
EP3828961B1
EP3828961B1 EP19841286.8A EP19841286A EP3828961B1 EP 3828961 B1 EP3828961 B1 EP 3828961B1 EP 19841286 A EP19841286 A EP 19841286A EP 3828961 B1 EP3828961 B1 EP 3828961B1
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positive electrode
mass
parts
negative electrode
electrolytic solution
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French (fr)
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EP3828961A4 (de
EP3828961A1 (de
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Keiko Kosuge
Fumio Kato
Toshiyuki Shimizu
Yusuke Kawahara
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a lithium primary cell and a smart meter.
  • Lithium primary cells have high energy density and low self-discharge property, and therefore they are used in many electronic devices. Lithium primary cells have an extremely long storage life, and can be stored at room temperatures for such a long time as ten years or more. Therefore, lithium primary cells are widely used as main power sources and memory back-up power sources in various meters.
  • a cylindrical lithium primary cell having a size of A or smaller is used as a power source of a gas meter.
  • the cylindrical lithium primary cell includes an electrode group including a positive electrode and a negative electrode wound with a separator interposed therebetween.
  • a lithium primary cell having such a spiral-structured electrode group has a high output property, and a large electric current can be taken out.
  • PTL 1 proposes a coin-type lithium primary cell in which low-crystalline manganese dioxide having a specific surface area of 8 to 28 m 2 /g and including boron and alkaline earth metal, is used for a positive electrode active material. This suppresses generation of gas during high-temperature storage.
  • PTL 2 discloses a lithium battery and PTL 3 discloses a lithium primary battery.
  • lithium primary cells having a large size and high capacity have been demanded as power sources for smart meters.
  • lithium primary cells having high capacity and having a spiral structured electrode group a problem of short-circuit current, which has not occurred in A-size and coin-type cells, may occur.
  • Specific examples of the problem include a problem that a large short-circuit current exceeding the allowable value may flow when an external short circuit occurs.
  • a lithium primary cell including an electrode group including a positive electrode, a negative electrode, and a separator, the positive electrode and the negative electrode being wound with the separator interposed between the positive electrode and the negative electrode; and a non-aqueous electrolytic solution, wherein in the electrode group, an area where the positive electrode and the negative electrode face each other is 250 cm 2 or more and 350 cm 2 or less, the positive electrode includes a positive electrode mixture including manganese dioxide and a boron compound, the negative electrode includes lithium metal or a lithium alloy, the non-aqueous electrolytic solution includes ethylene carbonate, a content of the boron compound in the positive electrode is 0.5 parts by mass or more and 2 parts by mass or less in terms of boron with respect to 100 parts by mass of the positive electrode mixture, and a content of the ethylene carbonate in the non-aqueous electrolytic solution is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the manganese dioxide.
  • a lithium primary cell including an electrode group including a positive electrode, a negative electrode, and a separator, the positive electrode and the negative electrode being wound with the separator interposed between the positive electrode and the negative electrode; and a non-aqueous electrolytic solution, wherein in the electrode group, an area where the positive electrode and the negative electrode face each other is 250 cm 2 or more and 350 cm 2 or less, the positive electrode includes a positive electrode mixture including manganese dioxide and a boron compound, the negative electrode includes lithium metal or a lithium alloy, the non-aqueous electrolytic solution includes ethylene carbonate, a mass ratio B/Mn of boron (B) included in the boron compound present in the positive electrode to manganese (Mn) included in the manganese dioxide present in the positive electrode is 0.009 or more and 0.036 or less, and a content of the ethylene carbonate in the non-aqueous electrolytic solution is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of
  • a short-circuit current at an external short circuit can be reduced.
  • FIG. 1 is a partially sectional front view of a lithium primary cell in accordance with one exemplary embodiment of the present invention.
  • a lithium primary cell in accordance with an exemplary embodiment of the present invention has high output and high capacity. That is to say, the lithium primary cell includes an electrode group including a positive electrode, a negative electrode, and a separator, the positive electrode and the negative electrode being wound with the separator interposed therebetween; and a non-aqueous electrolytic solution with which the electrode group is impregnated.
  • an area where the positive electrode and the negative electrode face each other is 250 cm 2 or more and 350 cm 2 or less.
  • the positive electrode includes a positive electrode mixture including manganese dioxide as a positive electrode active material.
  • the negative electrode includes lithium metal or a lithium alloy as a negative electrode active material.
  • the area where the positive electrode and the negative electrode face each other is an area in which an electrode reaction can proceed, and, usually, an area where lithium metal or a lithium alloy faces a positive electrode mixture layer including a positive electrode active material.
  • the positive electrode mixture includes a boron compound.
  • a content of the boron compound in the positive electrode is 0.5 parts by mass or more and 2 parts by mass or less in terms of boron with respect to 100 parts by mass of the positive electrode mixture.
  • in terms of boron means that an amount of a boron compound (part by mass) with respect to 100 parts by mass of the positive electrode mixture is converted into an amount of boron (parts by mass).
  • the non-aqueous electrolytic solution includes ethylene carbonate (EC).
  • a content of EC in the non-aqueous electrolytic solution is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of manganese dioxide.
  • a positive electrode including a predetermined amount of boron compound and a non-aqueous electrolytic solution including a predetermined amount of EC are used in combination, even if an area of facing the positive electrode and the negative electrode is large, such as 250 cm 2 or more, the short-circuit current when an external short circuit occurs can be reduced to be the allowable value or less.
  • the area of facing the positive electrode and the negative electrode is more than 350 cm 2 , even if the positive electrode includes a predetermined amount of boron compound, and the non-aqueous electrolytic solution includes a predetermined amount of EC, a short-circuit current when an external short circuit occurs may exceed the allowable value.
  • the short-circuit current is presumed to be reduced because use of a positive electrode including a predetermined amount of boron compound and a non-aqueous electrolytic solution including a predetermined amount of EC allows a good SEI (Solid Electrolyte Interface) film that suppresses a rapid electrode reaction to be appropriately formed on a surface of the positive electrode active material and the negative electrode active material.
  • SEI Solid Electrolyte Interface
  • the content of the boron compound in the positive electrode is less than 0.5 parts by mass in terms of boron with respect to 100 parts by mass of the positive electrode mixture, the effect of reducing the short-circuit current becomes smaller. Therefore, when the area of facing the positive electrode and the negative electrode is increased to 250 cm 2 or more, the short-circuit current may exceed the allowable value when an external short circuit occurs.
  • the short-circuit current may exceed the allowable value when an external short circuit occurs. This is presumed to be because the formation of a good SEI film is inhibited due to the imbalance of the reaction on a solid-liquid interface.
  • the mass ratio B/Mn of boron (B) to manganese (Mn) included in the positive electrode is, for example, 0.009 or more and 0.036 or less.
  • a lithium primary cell including an electrode group including a positive electrode, a negative electrode, and a separator, the positive electrode and the negative electrode being wound with the separator interposed between the positive electrode and the negative electrode; and a non-aqueous electrolytic solution, wherein in the electrode group, an area where the positive electrode and the negative electrode face each other is 250 cm 2 or more and 350 cm 2 or less, the positive electrode includes a positive electrode mixture including manganese dioxide and a boron compound, the negative electrode includes lithium metal or a lithium alloy, the non-aqueous electrolytic solution includes ethylene carbonate, a mass ratio B/Mn of boron (B) included in the boron compound present in the positive electrode to manganese (Mn) included in the manganese dioxide present in the positive electrode is 0.009 or more and 0.036 or less, and a content of the ethylene carbonate in the non-aqueous electrolytic solution is 1 part by mass or more and 10 parts by mass or less with respect to
  • the content of the boron compound in the positive electrode and the B/Mn ratio can be obtained by, for example, ICP optical emission spectrometry.
  • the content rate of boron derived from the boron compound in the positive electrode mixture layer and B/Mn can be obtained by the following procedures (i) to (iv).
  • a part of the boron compound included in the positive electrode mixture layer may be decomposed in the positive electrode, and a part of B in the boron compound may be incorporated into the manganese dioxide included in the positive electrode mixture layer.
  • B derived from the boron compound incorporated in the manganese dioxide also contributes to reduction of the short-circuit current when an external short circuit occurs.
  • the lithium salt of the non-aqueous electrolytic solution includes B
  • a part of the lithium salt of the non-aqueous electrolytic solution may be decomposed at the positive electrode, and a part of B of the lithium salt may be incorporated into the manganese dioxide included in the positive electrode mixture layer.
  • an amount of B derived from the lithium salt incorporated in the manganese dioxide is a minute amount and is a negligible level as compared with the amount of B derived from the boron compound included in the positive electrode mixture layer.
  • the above-mentioned W B is obtained as an amount of B derived from the boron compound included in the positive electrode mixture layer.
  • the effect of reducing a short-circuit current when an external short circuit occurs cannot be obtained.
  • the content of the boron compound in the positive electrode is preferably 1 part by mass or more and 2 parts by mass or less in terms of boron with respect to 100 parts by mass of the positive electrode mixture.
  • the boron compound a compound including a boron atom and an oxygen atom can be used. Since such a compound has water solubility, when the compound is used as an aqueous solution, it can be uniformly mixed with the positive electrode active material. On the other hand, the compound including a boron atom and an oxygen atom does not easily elute into the non-aqueous electrolytic solution and easily remains in the positive electrode.
  • the boron compound preferably includes at least one selected from the group consisting of, for example, H 3 BO 3 , B 2 O 3 , HBO 2 , H 4 B 2 O 4 , Li 3 BO 3 , LiBO 2 and Li 4 B 2 O 4 .
  • H 3 BO 3 is preferable.
  • the short-circuit current may exceed the allowable value when an external short circuit occurs.
  • the short-circuit current may exceed the allowable value when an external short circuit occurs. This is presumed to be because the formation of a good SEI film is inhibited due to the imbalance of the reaction at the solid-liquid interface.
  • the content of EC in the non-aqueous electrolytic solution is preferably 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of manganese dioxide.
  • the content of EC (the amount with respect to 100 parts by mass of manganese dioxide) in the non-aqueous electrolytic solution can be obtained by the following procedures (I) to (III).
  • the positive electrode includes a positive electrode current collector, and a positive electrode mixture layer attached to the positive electrode current collector.
  • the positive electrode mixture layer is formed, for example, on both surfaces of a sheet-like positive electrode current collector, such that the sheet-like positive electrode current collector is embedded.
  • the positive electrode mixture layer includes manganese dioxide and a boron compound.
  • the positive electrode mixture layer may include a conductive agent and/or a binder in addition to the manganese dioxide and the boron compound.
  • a conductive material such as a carbon material is used.
  • the binder for example, fluororesin is used.
  • the positive electrode current collector is, for example, an expanded metal, net, punching metal, or the like, made of stainless steel.
  • the positive electrode mixture layer is formed using, for example, a wet positive electrode mixture prepared by adding an appropriate amount of water to the manganese dioxide and the boron compound. To the positive electrode mixture, a conductive agent and a binder may further be added.
  • the negative electrode includes lithium metal or a lithium alloy.
  • the lithium metal or the lithium alloy is formed, for example, in a long sheet by extrusion molding, and is used as a negative electrode.
  • As the lithium alloy alloys such as Li-Al, Li-Sn, Li-Ni-Si, and Li-Pb are used, but a Li-Al alloy is preferable.
  • the content of metallic elements other than lithium, included in the lithium alloy is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of securing discharge capacity and stabilization of internal resistance.
  • a separator may be a porous sheet formed of an insulating material having resistance against the internal environment of a lithium primary cell. Specific examples thereof include a non-woven cloth made of synthetic resin and a microporous film made of synthetic resin, and the like.
  • the non-aqueous electrolytic solution includes a non-aqueous solvent, and lithium salt dissolved in the non-aqueous solvent.
  • the non-aqueous solvent includes at least EC.
  • the content of EC in the non-aqueous solvent is preferably, for example, 3% by volume or more and 33% by volume or less.
  • non-aqueous solvent in addition to EC, ⁇ -butyrolactone (GBL), propylene carbonate (PC), 1,2-dimethoxyethane (DME), and the like, can be used.
  • GBL ⁇ -butyrolactone
  • PC propylene carbonate
  • DME 1,2-dimethoxyethane
  • EC, PC, and DME are preferably 70% by volume or more in total amount with respect to the non-aqueous solvent.
  • lithium salt examples include lithium borofluoride, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium-bis(fluorosulfonyl)imide, lithium-bis(trifluoromethane sulfonyl)imide, and the like.
  • the lithium primary cell in accordance with the exemplary embodiment of the present invention is described further specifically.
  • the present invention is not limited to the below-mentioned exemplary embodiment.
  • FIG. 1 is a partial sectional front view of a cylindrical lithium primary cell in accordance with an exemplary embodiment of the present invention.
  • Cylindrical lithium primary cell 10 includes bandlike positive electrode 1 and bandlike negative electrode 2 made of a sheet of lithium metal or a lithium alloy. Positive electrode 1 and negative electrode 2 are spirally wound with separator 3 interposed therebetween to constitute a columnar electrode group.
  • An area of facing positive electrode 1 and negative electrode 2 in the electrode group is 250 cm 2 or more and 350 cm 2 or less.
  • the width of bandlike positive electrode 1 is, for example, 37 mm or more and 40 mm or less.
  • the length of bandlike positive electrode 1 is, for example, 370 mm or more and 520 mm or less.
  • the thickness of positive electrode 1 is, for example, 0.4 mm or more and 0.6 mm or less.
  • the width of bandlike negative electrode 2 is, for example, 34 mm or more and 37 mm or less.
  • the length of bandlike negative electrode 2 is, for example, 450 mm or more and 520 mm or less.
  • the thickness of negative electrode 2 is, for example, 0.15 mm or more and 0.25 mm or less.
  • Positive electrode 1 includes positive electrode current collector 1a, and a positive electrode mixture layer attached to positive electrode current collector 1a.
  • the positive electrode mixture layer includes at least a positive electrode mixture and a boron compound.
  • the content of the boron compound in positive electrode 1 is 0.5 parts by mass or more and 2 parts by mass or less in terms of boron with respect to 100 parts by mass of the positive electrode mixture.
  • An amount of the manganese dioxide included in the positive electrode mixture layer is, for example, 2.5 g or more and 3.2 g or less with respect to 1 cm 3 of the positive electrode mixture layer.
  • the electrode group together with a non-aqueous electrolytic solution are housed inside a metal case (cell can 9) having an opening and a bottom.
  • the non-aqueous electrolytic solution includes 1 part by mass or more and 10 parts by mass or less of EC with respect to 100 parts by mass of manganese dioxide.
  • the upper part and the lower part of the electrode group are provided with upper insulating plate 6 and lower insulating plate 7, respectively.
  • the metal case generally includes iron, stainless steel, and the like.
  • the inner diameter of the metal case is, for example, 23 mm or more and 25.5 mm or less.
  • Positive electrode 1 includes, in the vicinity of its center in the thickness direction, a sheet-like positive electrode current collector 1a. Positive electrode 1 has a part in which a portion of the positive electrode mixture layer is removed such that positive electrode current collector 1a is exposed, and one end of positive electrode tab lead 4 is welded to the exposed part. The other end of positive electrode tab lead 4 is welded to the inner surface of sealing plate 8 for sealing the opening of the cell can 9. One end of negative electrode tab lead 5 is welded to negative electrode 2. The other end of tab lead 5 is welded to the inner bottom surface of cell can 9.
  • the smart meter of the present invention includes a gas meter, a communication device, and the above-described lithium primary cell supplying the gas meter and the communication device with electric power.
  • ATEX Directive an external short circuit current for a gas meter is regulated at 5 A or less.
  • the lithium primary cell needs to supply not only a gas meter but also a communication device with electric power. Therefore, for the lithium primary cell to be used for power source of the smart meter is required to have high capacity.
  • the lithium primary cell in accordance with the present invention can obtain high capacity required to the smart meter, and can suppress the external short circuit current to 5 A or less.
  • use of the lithium primary cell in accordance with the present invention permits obtaining of a smart meter capable of sufficiently supplying the gas meter and the communication device with electric power, and conforming the ATEX Directive and being excellent in safety.
  • a wet positive electrode mixture was prepared by adding 5 parts by mass of Ketjen black as a conductive agent, 5 parts by mass of polytetrafluoroethylene as a binder, a boron compound, and a proper amount of pure water to 100 parts by mass of electrolytic manganese dioxide as a positive electrode active material, and kneading the resultant mixture.
  • Boric acid H 3 BO 3 was used for the boron compound.
  • the additive amount of the boron compound was 1.0 part by mass in terms of boron with respect to 100 parts by mass of the positive electrode mixture.
  • the mass ratio B/Mn of boron to manganese included in the positive electrode mixture was 0.018.
  • the wet positive electrode mixture together with positive electrode current collector 1a including expanded metal having a thickness of 0.3 mm and made of stainless steel were allowed to pass between a pair of rotating rollers rotating at a constant speed, thereby filling pores of the expanded metal with the positive electrode mixture, and covering both surfaces of the expanded metal with the positive electrode mixture layers to produce an electrode plate precursor.
  • the electrode plate precursor was dried, rolled by a roll press until the thickness became 0.4 mm, and cut into a predetermined size to obtain bandlike positive electrode 1.
  • the width of positive electrode 1 was 37 mm, and the length of positive electrode 1 was 450 mm.
  • a sheet-like Li-Al alloy (Al content: 0.1% by mass) having a thickness of 0.17 mm was cut into a predetermined dimension to obtain a bandlike negative electrode 2.
  • the width of negative electrode 2 was 34 mm, and the length of negative electrode 2 was 495 mm.
  • a positive electrode mixture material was removed from a portion of positive electrode 1 to expose a positive electrode current collector, and positive electrode lead 4 made of stainless steel was welded to the exposed part.
  • Negative electrode tab lead 5 made of nickel was welded to a predetermined section of negative electrode 2.
  • Positive electrode 1 and negative electrode 2 were spirally wound with separator 3 interposed therebetween to constitute a columnar electrode group having an area of facing the positive electrode and the negative electrode of 300 cm 2 .
  • separator 3 a microporous membrane (porosity: 40%) made of polyethylene and having a thickness of 38 pm was used.
  • a non-aqueous electrolytic solution was prepared by dissolving lithium trifluoromethanesulfonate as a lithium salt at a concentration of 0.2 mol/L in a solvent obtained by mixing propylene carbonate (PC) and 1,2-dimethoxyethane (DME) in a volume ratio of 2:1.
  • PC propylene carbonate
  • DME 1,2-dimethoxyethane
  • 5 parts by mass of ethylene carbonate (EC) with respect to 100 parts by mass of electrolytic manganese dioxide was added to the non-aqueous electrolytic solution. Note here that the volume ratio of EC with respect to the total of EC, PC, and DME was 16% by volume.
  • a cell of Example 1 is referred to as cell A1.
  • Cell B1 was produced in the same manner as in Example 1 except that a boron compound was not added to a positive electrode mixture, and EC was not added to a non-aqueous electrolytic solution, and the produced cell B1 was evaluated.
  • Cell B2 was produced in the same manner as in Example 1 except that EC was not added to a non-aqueous electrolytic solution, and the produced cell B2 was evaluated.
  • Cell B3 was produced in the same manner as in Example 1 except that the boron compound was not added to a positive electrode mixture, and the produced cell B3 was evaluated.
  • each content of the boron compound in the positive electrode shown in Table 1 and the below-mentioned Tables 2 to 5 is an amount (part by mass) in terms of boron with respect to 100 parts by mass of the positive electrode mixture.
  • each content of EC in the non-aqueous electrolytic solution is an amount (part by mass) with respect to 100 parts by mass of manganese dioxide.
  • the maximum short-circuit current is 5 A or less.
  • the maximum short-circuit current exceeds 5 A.
  • Cells B4 to B7 were produced in the same manner as in Comparative Example 1 except that a length of a positive electrode and a length of a negative electrode were adjusted such that an area of facing the positive electrode and the negative electrode in the electrode group became values shown in Table 2.
  • the evaluation results of cells B4 to B7 together with the evaluation result of cell B1 are shown in Table 2.
  • Cells A2 to A3 and cell B8 were produced in the same manner as in Example 1 except that a length of the positive electrode and a length of the negative electrode were adjusted such that an area of facing the positive electrode and the negative electrode in the electrode group became values shown in Table 3, and cells A2 to A3 and cell B8 were evaluated.
  • the evaluation results of A2 to A3 and cell B8 together with the evaluation result of cell A1 are shown in Table 3. [Table 2] Battery No.
  • the maximum short-circuit current is 5 A or less.
  • the area of facing the positive electrode and the negative electrode is less than 250 cm 2 , and therefore high capacity required to a smart meter cannot be obtained.
  • Cells A4 to A11 and cells B9 to B21 were produced in the same manner as in Example 1 except that each content of the boron compound in each positive electrode (an amount in terms of boron with respect to 100 parts by mass of a positive electrode mixture) was the value shown in Table 4; the ratios of B/Mn when the content of the boron compound in the positive electrode was 0.5 parts by mass, 1 part by mass, and 2 parts by mass were 0.009, 0.018, and 0.036, respectively; and each content of EC in the non-aqueous electrolytic solution was the values shown in Table 4.
  • the produced Cells A4 to A11 and cells B9 to B21 were evaluated.
  • the maximum short-circuit current is 5 A or less.
  • Cells A12 to A14 were produced in the same manner as in Example 1 except that compounds shown in Table 5 were used for a boron compound, and cells A12 to A14 were evaluated. Cells A12 to A14 had B/Mn of 0.018. The evaluation results of cells A12 to A14 together with evaluation results of cell A1 and cell B1 are shown in Table 5.
  • the maximum short-circuit current is 5 A or less.
  • a lithium primary cell in accordance with the present invention is suitably used as a power source of electronic devices such as a smart meter that requires, for example, excellent cell performance and high safety.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Primary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Claims (5)

  1. Lithium-Primärzelle (10), die Folgendes umfasst:
    eine Elektrodengruppe, die eine positive Elektrode (1), eine negative Elektrode (2) und einen Separator (3) umfasst, wobei die positive Elektrode (1) und die negative Elektrode (2) mit dem zwischen der positiven Elektrode (1) und der negativen Elektrode (2) angeordneten Separator (3) gewickelt sind; und
    eine wasserfreie elektrolytische Lösung,
    wobei in der Elektrodengruppe eine Fläche der positiven Elektrode und der negativen Elektrode, die einander zugewandt sind, 250 cm2 oder größer und 350 cm2 oder kleiner ist,
    wobei die positive Elektrode (1) ein Positivelektrodengemisch umfasst, das Mangandioxid und eine Borverbindung umfasst,
    die negative Elektrode (2) Lithiummetall oder eine Lithiumlegierung umfasst,
    die wasserfreie elektrolytische Lösung Ethylencarbonat umfasst,
    ein Gehalt der Borverbindung in der positiven Elektrode (1), was Bor betrifft, bezogen auf 100 Massenanteile des Positivelektrodengemischs, 0,5 Massenanteil oder mehr und 2 Massenanteile oder weniger beträgt.
    ein Gehalt des Ethylencarbonats in der wasserfreien elektrolytischen Lösung, bezogen auf 100 Massenanteile des Mangandioxids, 1 Massenanteil oder mehr und 10 Massenanteile oder weniger beträgt.
  2. Lithium-Primärzelle (10) nach Anspruch 1, wobei die Borverbindung ein Boratom und ein Sauerstoffatom umfasst.
  3. Lithium-Primärzelle (10) nach Anspruch 1 oder 2, wobei die Borverbindung mindestens eines umfasst, das ausgewählt ist aus der Gruppe, die besteht aus H3BO3, B2O3, HBO2, H4B2O4, Li3BO3, LiBO2 und Li4B2O4.
  4. Lithium-Primärzelle (10), die Folgendes umfasst:
    eine Elektrodengruppe, die eine positive Elektrode (1), eine negative Elektrode (2) und einen Separator (3) umfasst, wobei die positive Elektrode (1) und die negative Elektrode (2) mit dem zwischen der positiven Elektrode (1) und der negativen Elektrode (2) angeordneten Separator (3) gewickelt sind; und
    eine wasserfreie elektrolytische Lösung,
    wobei in der Elektrodengruppe eine Fläche der positiven Elektrode und der negativen Elektrode, die einander zugewandt sind, 250 cm2 oder größer und 350 cm2 oder kleiner ist,
    wobei die positive Elektrode (1) ein Positivelektrodengemisch umfasst, das Mangandioxid und eine Borverbindung umfasst,
    die negative Elektrode (2) Lithiummetall oder eine Lithiumlegierung umfasst,
    die wasserfreie elektrolytische Lösung Ethylencarbonat umfasst,
    ein Massenverhältnis B/Mn von Bor (B), das in der Borverbindung enthalten ist, die in der positiven Elektrode vorhanden ist, zu Mangan (Mn), das in dem Mangandioxid enthalten ist, das in der positiven Elektrode (1) vorhanden ist, 0,009 oder höher und 0,036 oder niedriger ist, und
    ein Gehalt des Ethylencarbonats in der wasserfreien elektrolytischen Lösung, bezogen auf 100 Massenanteile des Mangandioxids, 1 Massenanteil oder höher und 10 Massenanteile oder niedriger beträgt.
  5. Intelligenter Zähler, der einen Gaszähler, eine Kommunikationsvorrichtung und eine Lithium-Primärzelle (10) nach einem der Ansprüche 1 bis 4 umfasst, die den Gaszähler und die Kommunikationsvorrichtung mit elektrischer Leistung versorgt.
EP19841286.8A 2018-07-23 2019-04-02 Lithiumprimärzelle und intelligenter zähler Active EP3828961B1 (de)

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EP3828961A4 (de) 2021-09-08
JP6986710B2 (ja) 2021-12-22
EP3828961A1 (de) 2021-06-02
CN112470307A (zh) 2021-03-09
CN112470307B (zh) 2024-04-02
WO2020021775A1 (ja) 2020-01-30
JPWO2020021775A1 (ja) 2021-02-18

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